OCS binding to and reactivity with isolated gold cluster cations, Aun+ (n = 1-10), has been studied by infrared multiple photon dissociation (IR-MPD) spectroscopy in conjunction with quantum chemical calculations. The distribution of complexes AunSx(OCS)m+ formed reflects the relative reactivity of different cluster sizes with OCS, under the multiple collision conditions of our ablation source. The IR-MPD spectra of Aun(OCS)+ (n = 3-10) clusters are interpreted in terms of either μ1 or μ2 S binding motifs. Analysis of the fragmentation products following infrared excitation of parent Aun(OCS)+ clusters reveals strongly size-selective (odd-even) branching ratios for OCS and CO loss, respectively.  https://www.selleckchem.com/products/Erlotinib-Hydrochloride.html  CO loss signifies infrared-driven OCS decomposition on the cluster surface and is observed to occur predominantly on even n clusters (i.e., those with odd electron counts). The experimental data, including fragmentation branching ratios, are consistent with calculated potential energy landscapes, in which the initial species trapped are molecularly bound entrance channel complexes, rather than global minimum inserted structures. Attempts to generate Rhn(OCS)+ and Ptn(OCS)+ equivalents failed; only sulfide reaction products were observed in the mass spectrum, even after cooling the cluster source to -100 °C.Wormlike micelles (WLMs) are polymer-like chains formed by surfactant self-assembly in water. Recently, we have shown that WLMs can also be self-assembled in polar organic liquids like glycerol using a cationic surfactant and an aromatic salt. In this work, we focus on the dynamic rheology of the WLMs in glycerol and demonstrate that their rheology is very different from that of WLMs in water. Aqueous WLMs that are entangled into transient networks exhibit the rheology of a perfect Maxwell fluid having a single relaxation time tR-thereby, their elastic modulus G' and viscous modulus G″ intersect at a crossover frequency ωc = 1/tR. WLMs in glycerol also form entangled networks, but they are not Maxwell fluids; instead, they exhibit a double-crossover of G' and G″ (at ωc1 and ωc2) within the ω-window accessible by rheometry (10-2 to 102 rad/s). The first crossover at ωc1 (∼1 rad/s) corresponds to the terminal relaxation time (i.e., the timescale for chains to disentangle from the transient network and relax by reptation). At the other extreme, at frequencies above ωc2 (which is ∼10 rad/s), the rheology is dominated by the segmental motion of the chains. This "breathing regime" has rarely been accessed via experiments for aqueous WLMs because it falls around 105 rad/s. We believe that glycerol, a solvent that is much more viscous than water, exerts a crucial influence in pushing ωc2 to 1000-fold lower frequencies. On the basis of the rheology, we also hypothesize that WLMs in glycerol are shorter and weakly entangled compared to WLMs in water. Moreover, we suggest that WLMs in glycerol are "unbreakable" chains-i.e., the chains remain mostly intact instead of breaking and re-forming frequently-and this polymer-like behavior explains why the samples are quite unlike Maxwell fluids.While aryl germanes have recently found usage as coupling partners in powerful catalytic applications, the synthetic access to this promising functionality is currently limited. This report details the straightforward synthesis of functionalized aryl triethylgermanes via formal C-H functionalization. Building on the concept of directing-group-free and site-selective C-H functionalization of arenes to thianthrenium salt intermediates, we showcase their efficient couplings with triethylgermane (Et3Ge-H) at room temperature, which was enabled by the air- and moisture-stable Pd(I) dimer, [Pd(μ-I)(PtBu3)]2. The method tolerates numerous functional groups, including valuable (pseudo)halides.Externally added ligands were first found to have a significant impact on the Rh-catalyzed C-H-active [3 + 2] annulation of ketimines and alkynes. Olefin ligands have shown remarkable promotion effect for this reaction. The olefin promoted the reaction by increasing both the turnover rate and conversion of [Cp*RhCl2]2 in the formation of rhodacycle in the C-H activation step.Combining experimental and ab initio core-level photoelectron spectroscopy (periodic DFT and quantum chemistry calculations), we elucidated how ammonia molecules bond to the hydroxyls of the (H,OH)-Si(001) model surface at a temperature of 130 K. Indeed, theory evaluated the magnitude and direction of the N 1s (and O 1s) chemical shifts according to the nature (acceptor or donor) of the hydrogen bond and, when confronted to experiment, showed unambiguously that the probe molecule makes one acceptor and one donor bond with a pair of hydroxyls. The consistency of our approach was proved by the fact that the identified adsorption geometries are precisely those that have the largest binding strength to the surface, as calculated by periodic DFT. Real-time core-level photoemission enabled measurement of the adsorption kinetics of H-bonded ammonia and its maximum coverage (0.37 ML) under 1.5 × 10-9 mbar. Experimental desorption free energies were compared to the magnitude of the adsorption energies provided by periodic DFT calculations. Minority species were also detected on the surface. As in the case of H-bonded ammonia, DFT core-level calculations were instrumental to attribute these minority species to datively bonded ammonia molecules, associated with isolated dangling bonds remaining on the surface, and to dissociated ammonia molecules, resulting largely from beam damage.Soft magnetic materials have shown promise in diverse applications due to their fast response, remote actuation, and large penetration range for various conditions. Herein, a new soft magnetic composite material capable of reprogramming its magnetization profile without changing intrinsic magnetic properties of embedded magnetic particles or the molecular property of base material is reported. This composite contains magnetic microspheres in an elastomeric matrix, and the magnetic microspheres are composed of ferromagnetic microparticles encapsulated with oligomeric-PEG. By controlling the encapsulating polymer phase transition, the magnetization profiles of the magnetic composite can be rewritten by physically realigning the ferromagnetic particles. Diverse magnetic actuators with reprogrammable magnetization profiles are developed to demonstrate the complete reprogramming of complex magnetization profile.